Unsaturated group-containing amino resins, resin compositions, varnishes, prepregs, laminates, thermosetting molding materials, and adhesives

Abstract

Providing an unsaturated group-containing amino resin from which a cured product with a low dielectric tangent can be obtained. 【Solution means】The unsaturated group-containing amino resin contains a structure represented by formula (1). n is an integer of 1 or more, and R 1 is a group represented by formula (2), and R 2 is a crosslinking group. R 3 is an organic group having at least one unsaturated group selected from the group consisting of a vinylbenzyl group, an alkenyl group having 2 to 20 carbon atoms, an acryloyl group, and a methacryloyl group, or a hydrogen atom, and Ar 1 is a phenylene group or a naphthylene group, and Ar 2 is a phenylene group, a naphthylene group, or a group represented by formula (3). R 4 is the organic group having the unsaturated group or a hydrogen atom, and Ar 3 and Ar 4 are each independently a phenylene group or a naphthylene group. R 3 and R 4 In at least a part of them, they are organic groups having the unsaturated group. [Chemical formula 1] TIFF2026092925000027.tif29170

Description

[Technical Field]

[0001] The present invention relates to unsaturated group-containing amino resins, resin compositions, varnishes, laminates, prepregs, thermosetting molding materials, and adhesives. [Background technology]

[0002] Conventionally, cured epoxy resins have been used as insulating materials for components used in electronic products, such as insulating laminates and laminates in which copper foil is laminated on one or both sides (copper-clad laminates). Laminates are manufactured by impregnating a fibrous substrate with a varnish in which epoxy resin, a curing agent, etc., is dissolved in a solvent, drying it to form a prepreg, and then heat-pressing it individually or in multiple layers. Phenolic resin is widely used as a curing agent for epoxy resins. In recent years, as the performance of electronic products has been improved, insulating materials are required to have even lower dielectric loss tangents.

[0003] Patent Document 1 discloses a curable resin composition comprising a vinyl compound in which the terminals of a bifunctional phenylene ether oligomer having a polyphenylene ether skeleton in the molecule are modified with styrene, and a silane compound. Patent Document 2 discloses a thermosetting resin composition comprising a copolymer resin having structural units derived from an aromatic vinyl compound and structural units derived from maleic anhydride, an epoxy-modified polybutadiene having hydroxyl groups at both ends of the molecule, an active ester compound, and one or more selected from the group consisting of maleimide compounds and their modified products. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2009-179730 [Patent Document 2] Japanese Patent Publication No. 2018-165340 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, the dielectric loss tangent of the cured product of the curable resin composition described in Patent Document 1 is 0.0027 at 10 GHz, which is not sufficient. Furthermore, in conventional epoxy resin-phenol resin curing systems, hydroxyl groups are generated during curing, resulting in good adhesion to other materials (copper foil, fibrous substrates, etc.). However, in the curing system described in Patent Document 1, polar groups such as hydroxyl groups are not generated, so the resulting cured product has insufficient adhesion to other materials. The thermosetting resin composition described in Patent Document 2 exhibits good adhesion to other materials because hydroxyl groups are generated upon curing, but its dielectric loss tangent is insufficient.

[0006] The present invention has been made in view of the above circumstances, and aims to provide an unsaturated group-containing amino resin that yields a cured product with a low dielectric loss tangent, a resin composition using the same, a varnish, a prepreg, a laminate, a thermosetting molding material, and an adhesive. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] The following formula (1): [ka] (In equation (1), n ​​is an integer greater than or equal to 1, R 1 The following equation (2): [ka] [In formula (2), R 3 This is an organic group having at least one unsaturated group selected from the group consisting of vinylbenzyl group, alkenyl group having 2 to 20 carbon atoms, acryloyl group and methacryloyl group, or a hydrogen atom, Ar 1 is a phenylene group or a naphthylene group, and Ar 2 is a phenylene group, a naphthylene group, or the following formula (3): [ka] [In formula (3), R4 is an organic group having the unsaturated group or a hydrogen atom, and Ar 3 and Ar 4 are each independently a phenylene group or a naphthylene group.] is a group represented by.〕 is a group represented by, and R 2 is a crosslinking group. When n is 2 or more, n R 1 may be the same or different, and n R 2 may be the same or different.) includes a structure represented by, in the structure represented by the formula (1), R 3 and R 4 at least a part of which is an organic group having the unsaturated group, an unsaturated group-containing amino resin. [2] In the formula (1), n is an integer of 2 or more, in the structure represented by the formula (1), R 3 and R 4 a part of which is a hydrogen atom, the unsaturated group-containing amino resin according to [1]. [3] R 2 in the formula (1) is the following formula (5): [Chemical formula] (In the formula (5), R 5 and R 6 are each independently a hydrogen atom, a cycloalkyl group having 3 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an aryl group having 6 to 16 carbon atoms or a heterocyclic group having 3 to 16 carbon atoms, or R 5 and R 6 together with the carbon atom to which they are attached form a ring, the cycloalkyl group, the aryl group and the heterocyclic group may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a carboxy group and a hydroxyl group.) A base represented by the following formula (6): [ka] (In formula (6), R 7 , R 8 , R 9 and R 10 (Each of these is independently either a hydrogen atom or a methyl group.) An unsaturated group-containing amino resin as described in [1] or [2], wherein the group is represented by . [4] R in formula (1) above 2 This is represented by equation (5) above, and R in equation (5) above 5 is a hydrogen atom, and R 6 The unsaturated group-containing amino resin according to [3], wherein is a cycloalkyl group, an alkyl group, or an aryl group, or a group represented by formula (6). [5] Ar in formula (2) above 1 and Ar 2 Each of the following is a phenylene group, and is an unsaturated group-containing amino resin as described in any of [1] to [4]. A resin composition comprising an unsaturated group-containing amino resin described in any of [6][1] to [5] and an unsaturated group-containing compound other than the said unsaturated group-containing amino resin. [7] The resin composition according to [6], wherein the unsaturated group-containing compound is at least one selected from the group consisting of maleimide group-containing compounds and butadiene-styrene oligomers. A varnish comprising the resin composition described in [8], [6], or [7], and a solvent. [9] A prepreg comprising a fibrous substrate, the resin composition described in [6] or [7], and a curing accelerator. A laminate containing the cured prepreg described in

[10] [9]. A thermosetting molding material comprising the resin composition described in

[11] [6] or [7], a curing accelerator, and an inorganic filler. An adhesive comprising the resin composition described in

[12] [6] or [7], a curing accelerator, and an inorganic filler. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide an unsaturated group-containing amino resin that yields a cured product with a low dielectric loss tangent, a resin composition using the same, a varnish, a prepreg, a laminate, a thermosetting molding material, and an adhesive. [Modes for carrying out the invention]

[0009] [Unsaturated group-containing amino resin] An unsaturated group-containing amino resin according to one embodiment of the present invention includes a structure represented by the following formula (1) (hereinafter also referred to as structure (1)).

[0010] [ka]

[0011] In equation (1), n ​​is an integer greater than or equal to 1, and R 1 R is a group represented by the following formula (2) (hereinafter also referred to as group (2)), and 2 is a crosslinking group. If n is 2 or more, there are n R 1 The Rs may be the same or different, and there are n Rs. 2 They may be the same or different.

[0012] [ka]

[0013] In formula (2), R 3 This is an organic group or hydrogen atom having an unsaturated group, and Ar 1 is a phenylene group or a naphthylene group, and Ar 2 This is a phenylene group, a naphthylene group, or a group represented by the following formula (3) (hereinafter also referred to as group (3)).

[0014] [ka]

[0015] In formula (3), R 4 This is an organic group or hydrogen atom having an unsaturated group, and Ar 3and Ar 4 These are, independently, either a phenylene group or a naphthylene group.

[0016] Structure (1) consists of n R 1 Because it has n R 3 R including n or fewer 4 It may include. R in structure (1) 3 and R 4 At least a portion of it is an organic group having an unsaturated group. Structure (1) is R 4 If it does not include R 3 At least a portion of these are organic groups that have an unsaturated group.

[0017] In structure (1), n ​​is an integer greater than or equal to 2, and R in structure (1) 3 and R 4 It is preferable that a portion of it consists of hydrogen atoms. 3 and R 4 If part of it is a hydrogen atom, the presence of the polar group -NH- in structure (1) results in good adhesion between the cured product of the unsaturated group-containing amino resin or resin composition containing it and other materials (e.g., metals such as copper, aluminum, and iron).

[0018] R in structure (1) 3 and R 4 R, an organic group having an unsaturated group, is included in the total of 100 mol%. 3 and R is an organic group having an unsaturated group. 4 The total percentage of unsaturated groups (hereinafter also referred to as the unsaturated group modification rate) is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and even more preferably 15 to 60 mol%. When the unsaturated group modification rate is above the lower limit, the curability of the unsaturated group-containing amino resin and the thermophysical properties of the cured product tend to be superior. When the unsaturated group modification rate is below the lower limit, unreacted unsaturated groups and the like tend to remain less after curing, and the electrical properties tend to be superior. In addition, adhesion to other materials tends to be superior. The rate of unsaturated group denaturation is C 13 - Determined by NMR. Note that R in structure (1) 3 and R4 The value obtained by subtracting the unsaturated group denaturation rate from the total 100 mol% is R in structure (1). 3 and R 4 R, which is a hydrogen atom, is part of the total 100 moles. 3 and hydrogen atoms R 4 This corresponds to the total proportion.

[0019] <n> n is an integer greater than or equal to 1, and its value depends on the molecular weight of the unsaturated group-containing amino resin. n is R 1 Ya R 2 Depending on the structure, for example, 1 to 500 is preferred, and 1 to 300 is more preferred. When n is within this range, the weight-average molecular weight of the unsaturated group-containing amino resin tends to fall within the preferred range described later.

[0020] <R 1 (Group(2))> R 3 and R 4 The unsaturated group in is at least one selected from the group consisting of vinylbenzyl group, alkenyl group having 2 to 20 carbon atoms, acryloyl group, and methacryloyl group. The alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 to 15. Specific examples of alkenyl groups include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl groups. As for alkenyl groups, CH2=CH-R a -A group represented by R is preferred. a R is a single bond or an alkylene group with 1 to 18 carbon atoms. a It can be linear or branched. a The number of carbon atoms is preferably 1 to 13.

[0021] An organic group having an unsaturated group may consist solely of an unsaturated group, or it may consist of an unsaturated group and a linking group. The linking group connects the nitrogen atom in formula (3) or (4) to the unsaturated group. Examples of linking groups include -Ph-CH2- (where Ph is a phenylene group) and carbonyl groups.

[0022] Ar in base (2) 1 and Ar 2 Examples of combinations include the following: Combination 1: Ar 1 and Ar 2 is each a phenylene group. Combination 2: Ar 1 is a phenylene group, Ar 2 is a naphthylene group. Combination 3: Ar 1 and Ar 2 are each a phenylene group. Combination 4: Ar 1 is a phenylene group, Ar 2 is group (3) and Ar 3 and Ar 4 are each a group that is a phenylene group. Combination 5: Ar 1 is a naphthylene group, Ar 2 is group (3) and Ar 3 is a phenylene group, Ar 4 is a group that is a naphthylene group. Among these, from the viewpoints of the softening point and melt viscosity of the product, combination 1 is preferred.

[0023] <R 2 > R 2 The crosslinking group of R is not particularly limited, and examples thereof include a group represented by the following formula (5) (hereinafter also referred to as group (5)), and a group represented by the following formula (6) (hereinafter also referred to as group (6)). Among these, group (5) is preferred in terms of the glass transition temperature of the cured product becoming higher. Group (6) is preferred in terms of the heat resistance, flame retardancy, and dielectric properties of the resin being more excellent.

[0024]

Chemical formula

[0025] In formula (5), R 5 and R 6 are each independently a hydrogen atom, a cycloalkyl group having 3 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms, an aryl group having 6 to 16 carbon atoms, or a heterocyclic group having 3 to 16 carbon atoms, or R 5 and R 6 It forms a ring together with the carbon atom to which it is bonded. The cycloalkyl group, aryl group, and heterocyclic group may each have at least one substituent selected from the group consisting of a halogen atom, nitro group, amino group, alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, alkenyloxy group having 2 to 10 carbon atoms, carboxy group, and hydroxy group.

[0026]

Chemical formula

[0027] In formula (6), R 7 , R 8 , R 9 and R 10 are each independently a hydrogen atom or a methyl group.

[0028] R 5 and R 6 In, the cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group is preferably 3 to 15. When the cycloalkyl group has a substituent, the number of substituents may be one or two or more. The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 15. The alkenyl group may be linear or branched. The number of carbon atoms of the alkenyl group is preferably 2 to 15. As the alkenyl group, a group represented by CH2=CH-R b - is preferred. R b is a single bond or an alkylene group having 1 to 13 carbon atoms. R b may be linear or branched. The number of carbon atoms of R b is preferably ~10. The aryl group may be monocyclic or polycyclic. The number of carbon atoms of the aryl group is preferably 6 to 16. When the aryl group has a substituent, the number of substituents may be one or two or more. Heterocyclic groups have heteroatoms (atoms other than carbon atoms) in their ring skeleton. Examples of heteroatoms include oxygen, nitrogen, and sulfur atoms. Heterocyclic groups can be monocyclic or polycyclic. Specific examples of heterocyclic groups include groups obtained by removing one hydrogen atom from a heterocycle, such as furan, thiophene, pyrrole, pyridine, quinoline, coumarin, benzofuran, acridine, phenoxazine, and phenothiazine. If a heterocyclic group has substituents, the number of substituents can be one or two or more. Preferred substituents for cycloalkyl groups, aryl groups, and heterocyclic groups are alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and alkenyloxy groups having 2 to 10 carbon atoms.

[0029] As a basis (5), from the standpoint of electrical characteristics, R 5 is a hydrogen atom, and R 6 The group is preferably a cycloalkyl group, an alkyl group, or an aryl group. The cycloalkyl group and aryl group may have the substituents described above. Examples of alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl Examples include ethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-ethyl-pentyl group, n-octyl group, n-nonyl group, 2,3-dimethylheptyl group, and n-decyl group. Examples of cycloalkyl groups include cyclobutyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, cyclopentyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl group, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethylcyclobutyl group, 2-ethylcyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, and 1,3-dimethylcyclobutyl group. Examples include 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group, and 3-methylcyclohexyl group. Examples of aryl groups include phenyl, tolyl, methoxyphenyl, isopropylphenyl, biphenyl, naphthyl, and phenanthryl groups. Of these, alkyl groups or cycloalkyl groups are preferred in terms of the resin's tendency to have low dielectric properties, reduced viscosity, and superior handling and solvent solubility. Cyclohexyl groups, methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, t-butyl groups, i-butyl groups, n-pentyl groups, n-octyl groups, n-nonyl groups, 2,3-dimethylheptyl groups, and n-decyl groups are more preferred. On the other hand, aryl groups are preferred in terms of superior heat resistance, flame retardancy, and solvent solubility of the resin.

[0030] <Characteristics of unsaturated group-containing amino resins> The weight-average molecular weight (Mw) of the unsaturated group-containing amino resin is preferably 500 to 100,000, more preferably 500 to 50,000, and even more preferably 700 to 30,000. When Mw is above the lower limit, handling properties are good, and when it is below the upper limit, solvent solubility is good. The molecular weight dispersion (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) of the unsaturated group-containing amino resin, is preferably 1.3 or higher, and more preferably 1.5 or higher. Mw and Mn are values ​​equivalent to standard polystyrene, measured by gel permeation chromatography (GPC).

[0031] The unsaturated group equivalent of the unsaturated group-containing amino resin is preferably 100 to 3000 g / eq, more preferably 150 to 2500 g / eq, and even more preferably 200 to 2000 g / eq. When the unsaturated group equivalent is above the lower limit, the dielectric properties are good, and when it is below the upper limit, the heat resistance is good. The unsaturated group equivalent is C 13 -This is a theoretical value (theoretical unsaturated group equivalent) determined by NMR.

[0032] <Method for producing unsaturated group-containing amino resin> An unsaturated group-containing amino resin can be produced, for example, by reacting an amino resin having the structure represented by the following formula (11) with the aforementioned modifying agent having an unsaturated group.

[0033] [ka]

[0034] In equation (11), n ​​is an integer greater than or equal to 1, and R 11 R is a group represented by the following formula (12) (hereinafter also referred to as group (12)), 2 is a crosslinking group. If n is 2 or more, there are n R 11 The Rs may be the same or different, and there are n Rs. 2 They may be the same or different.

[0035] [ka]

[0036] In formula (2), Ar 1 is a phenylene group or a naphthylene group, and Ar 5 This is a phenylene group, a naphthylene group, or a group represented by the following formula (13) (hereinafter also referred to as group (13)).

[0037] [ka]

[0038] In formula (13), Ar 3 and Ar 4 These are, independently, either a phenylene group or a naphthylene group.

[0039] [Amino resin] Amino resin is R 3 and R 4 It is the same as the unsaturated group-containing amino resin described above, except that all of the atoms are hydrogen atoms. When an amino resin is modified with a compound containing an unsaturated group, at least some of the hydrogen atoms bonded to the nitrogen atom in the amino resin become organic groups containing an unsaturated group, resulting in an unsaturated group-containing amino resin.

[0040] Amino resins can be manufactured by known methods. For example, an aromatic secondary amine compound represented by the following formula (21) and R 2 The desired amino resin can be obtained by reacting it with a crosslinking agent having a corresponding structure.

[0041] [ka]

[0042] R 11 This is as stated above. Specific examples of aromatic secondary amine compounds include diphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, N,N'-diphenyl-1,4-phenylenediamine, and N,N'-di-2-naphthyl-1,4-phenylenediamine. Aromatic secondary amine compounds may be used individually or in combination of two or more.

[0043] Examples of crosslinking agents include aldehyde compounds represented by the following formula (22), diene compounds represented by the following formula (23), and dialkoxymethyl compounds. The R of the amino resin obtained using the above aldehyde compound as a crosslinking agent 2 R 5 The group (5) is a hydrogen atom. The R of the amino resin obtained using the above diene compound as a crosslinking agent 2 R 8 and R 10 This becomes a methyl group (6).

[0044] [ka]

[0045] R 6 This is as stated above. Specific examples of aldehyde compounds represented by formula (22) include cyclohexanecarboxyaldehyde, hexanal, heptanal, octanal, 3,5,5-trimethylhexanal, nonanal, decenal, 10-undecenal, 2-allyloxybenzaldehyde, 4-isobutylbenzaldehyde, 4-tert-butylbenzaldehyde, 3,4-dimethoxybenzaldehyde, cuminaldehyde, and the like. Aldehyde compounds may be used individually or in combination of two or more.

[0046] [ka]

[0047] R 7 and R 9 This is as stated above. Specific examples of diene compounds include 1,3-divinylbenzene, 1,4-divinylbenzene, and 1,4-diisopropenylbenzene. Diene compounds may be used individually or in combination of two or more.

[0048] The molar ratio of the crosslinking agent to the aromatic secondary amine compound (crosslinking agent / aromatic secondary amine compound) is preferably 0.33 to 5.0, and more preferably 0.50 to 3.0. If this molar ratio is above the lower limit, the molecular weight of the product increases, improving handling properties. If this molar ratio is below the upper limit, gelation during the reaction can be suppressed, and a solvent-soluble resin can be obtained.

[0049] The reaction between the aromatic secondary amine compound and the crosslinking agent is preferably carried out in the presence of a catalyst. As for the catalyst, there are no particular restrictions once the reaction proceeds, and it can be appropriately selected depending on the type of crosslinking agent. When the crosslinking agent is the above-mentioned aldehyde compound or the above-mentioned diene compound, an acid catalyst can be used as a catalyst. Examples of acid catalysts include mineral acids such as sulfuric acid, phosphoric acid, and hydrochloric acid; sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, and trifluoroacetic acid; and carboxylic acids such as formic acid, oxalic acid, and oxalic acid dihydrate. The amount of acid catalyst used is preferably 1.0 to 0.00001% by mass, and more preferably 0.1 to 0.0001% by mass, relative to the mass of the aromatic secondary amine compound. If the amount used is above the lower limit, the reaction rate increases, and the resin is more easily obtained. If the amount used is below the upper limit, turbidity is less likely to occur in the resulting resin.

[0050] The reaction between the aromatic secondary amine compound and the crosslinking agent may be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the resulting resin. Examples include toluene, xylene, tetrahydrofuran, anisole, 1-methoxy-2-propanol, propylene glycol monomethyl ether acetate, and cyclopentyl methyl ether. One solvent may be used alone, or two or more solvents may be used in combination.

[0051] The reaction temperature is, for example, 15 to 200°C, and more preferably 40 to 180°C. When the crosslinking agent is the above-mentioned aldehyde compound, 50 to 170°C is preferred, and 60 to 150°C is more preferred. When the crosslinking agent is the above-mentioned diene compound, 50 to 190°C is preferred, and 60 to 180°C is more preferred. If the reaction temperature is above the lower limit, the reaction proceeds easily. If the reaction temperature is below the upper limit, side reactions are less likely to occur, and the desired resin is more easily obtained. The reaction time can be adjusted as needed depending on the reaction temperature, but it is typically between 1 and 48 hours. After the reaction, neutralization, reprecipitation, washing, drying, and other treatments may be carried out as needed.

[0052] [Denaturant] Examples of denaturing agents include R 12 Examples of compounds represented by -X include R 12 A is an organic group having an unsaturated group, and X is a halogen atom. Organic groups having an unsaturated group are as described above. Examples of halogen atoms include chlorine and bromine atoms. Specific examples of denaturing agents include halomethylstyrene such as chloromethylstyrene (AGC Seimi Chemical Co., Ltd.: CMS-P, CMP-14); halogenated alkenyls such as allyl chloride, allyl bromide, 5-bromo-1-pentene, 2-methylallyl chloride, 7-octenyl bromide, 3-chloro-1-butene, 4-chloro-1-butene, 6-chloro-1-hexene, 4-bromo-1-butene, 6-bromo-1-hexene, and 10-bromo-1-decane; and 3-chloro-1-propyne, 3-bromo-1-propyne, 1-chloro-2-pentine, 1-bromo-2-pentine, cryoyl chloride, methacryloyl chloride, and crotonoyl chloride. A single denaturing agent may be used alone, or two or more may be used in combination. The modifier used can be appropriately changed depending on the conditions for curing the unsaturated group-containing amino resin. For example, when halomethylstyrene is used, the resulting unsaturated group-containing amino resin can be cured at low temperatures or without a catalyst, but tends to have poor handling properties due to the low curing temperature. On the other hand, alkenyl halides require a catalyst for curing, but tend to have excellent handling properties when mixing the resin due to their high curing temperature.

[0053] [Reaction between amino resin and modifier] An unsaturated group-containing amino resin can be obtained by reacting an amino resin with a modifying agent. The reaction between the amino resin and the modifying agent is preferably carried out in the presence of a catalyst. As a catalyst, there are no particular restrictions as long as the reaction proceeds. Examples include sodium hydroxide, potassium hydroxide, magnesium metal, alkyl zinc compounds (such as di-n-butylzinc), lithium hydroxide, lithium acetate, titanium esters (such as tetra-n-butyl titanate), zinc oxide, lead oxide, manganese dioxide, tetraalkyl orthotitanate, zinc acetate, antimony oxide, germanium oxide, alkoxides (such as potassium-t-butoxide and sodium methoxide), alkali metals (such as lithium and sodium), alkali metal hydrides (such as lithium hydride and sodium hydride), alkali metal hydroxides (such as lithium hydroxide and sodium hydroxide), and metal halides.

[0054] The reaction between the amino resin and the modifying agent is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction and dissolves the resulting resin. Examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethyl lactate, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, tetrahydrofuran, cyclopentyl methyl ether, and N,N-dimethylacetamide. One solvent may be used alone, or two or more may be used in combination.

[0055] The reaction temperature is, for example, 10°C to 120°C, or even 20°C to 110°C. If the reaction temperature is above the lower limit, the reaction proceeds easily. If the reaction temperature is below the upper limit, side reactions are less likely to occur, and the desired resin is more easily obtained. The reaction time can be adjusted as needed depending on the reaction temperature, but it is typically between 1 and 48 hours. After the reaction, neutralization, reprecipitation, washing, drying, and other treatments may be carried out as needed.

[0056] The unsaturated group-containing amino resin of this embodiment can be cured using a curing system that does not generate hydroxyl groups during curing (for example, a curing system using other unsaturated group-containing compounds such as maleimide group-containing compounds) because it contains unsaturated groups. Curing can be performed by heating. The cured product obtained by curing the unsaturated group-containing amino resin of this embodiment using the curing system exhibits excellent electrical properties and low water absorption. Furthermore, it also possesses good heat resistance and mechanical properties.

[0057] The unsaturated group-containing amino resin of this embodiment can be cured independently by the reaction of unsaturated groups within the amino resin, even without being combined with an unsaturated group-containing compound. However, by combining it with other unsaturated group-containing compounds, the curing temperature can be lowered compared to curing it alone, and thermal properties such as the glass transition temperature can be improved. Therefore, it is preferable to subject it to the curing reaction in combination with an unsaturated group-containing compound.

[0058] There are no particular limitations on the applications of unsaturated group-containing amino resins. For example, their applications may be the same as those of known thermosetting molding materials, such as encapsulating materials, film materials, and laminating materials. More specific examples of applications include semiconductor encapsulating materials, resin materials for encapsulating electronic components, electrical insulating materials, resin materials for copper-clad laminates, build-up laminate materials, resist materials, resin materials for liquid crystal color filters, paints, various coatings, adhesives, and fiber-reinforced plastic (FRP) materials.

[0059] [Resin composition] A resin composition according to one embodiment of the present invention comprises the unsaturated group-containing amino resin described above and an unsaturated group-containing compound other than the unsaturated group-containing amino resin described above (hereinafter also referred to as "other unsaturated group-containing compound").

[0060] Other unsaturated group-containing compounds have one or more unsaturated groups. From the viewpoint of the cured properties of the cured product, it is preferable that the number of unsaturated groups in the other unsaturated group-containing compounds be two or more. Examples of unsaturated groups include maleimide groups, alkenyl groups with 2 to 20 carbon atoms, acryloyl groups, methacryloyl groups, and propargyl groups.

[0061] As for other unsaturated group-containing compounds, at least one selected from the group consisting of maleimide group-containing compounds and butadiene-styrene oligomers is preferred from the viewpoint of heat resistance and dielectric properties of the molded product. Examples of maleimide group-containing compounds include bismaleimide compounds and polyphenylmethanemaleimide. Examples of bismaleimide compounds include alkylbismaleimide, diphenylmethanebismaleimide, phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, and 1,3-bis(4-maleimidophenoxy)benzene. Polyphenylmethanemaleimide is a polymer in which three or more benzene rings, each substituted with a maleimide group, are linked via methylene groups. An example of polyphenylmethanemaleimide is BMI-2300, manufactured by Yamato Chemical Industries, Ltd. Examples of butadiene-styrene oligomers include styrene-butadiene, styrene-butadieneethylene, styrene-butadienestyrene, and styrene-ethylene-butylenestyrene. The number-average molecular weight of butadiene-styrene oligomers is, for example, 1,000 to 10,000.

[0062] Other unsaturated group-containing compounds include the following: Asenaphthylene N-vinyl-2-pyrrolidone, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, ethylene oxide adduct methacrylate of bisphenol A, trimethylolpropane trimethacrylate, tricyclodecane dimethanol dimethacrylate, glycerin dimethacrylate, trimethylolpropane trimethacrylate, ethoxylated isocyanurate triacrylate, ε-caprolactone modified tris-(2-acryloxyethyl) Examples include socianurates, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, divinyl isophthalate, polyphenylene ether modified with methacryloyl groups at both ends (product name SA-9000, manufactured by Sabic LLC), polyphenylene ether modified with styrene-royl groups at both ends (product name OPE-2St, manufactured by Mitsubishi Gas Chemical Company, Inc.), polyisoprene, polybutadiene, butyl rubber, ethylene propylene rubber, styreneisoprenestyrene, styrenepropylenestyrene, styreneethylenepropylenestyrene, etc.

[0063] In the resin composition, the content of other unsaturated group-containing compounds is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and even more preferably 20 to 80% by mass, based on the total mass of the unsaturated group-containing amino resin and the other unsaturated group-containing compounds. When the content of other unsaturated group-containing compounds is above the lower limit, the heat resistance tends to be better. When the content of other unsaturated group-containing compounds is below the upper limit, the dielectric properties tend to be better.

[0064] The resin composition can be produced, for example, by mixing an unsaturated group-containing amino resin with another unsaturated group-containing compound. The mixing of each component can be carried out by conventional methods. After mixing the unsaturated group-containing amino resin with another unsaturated group-containing compound, the unsaturated group-containing amino resin and the other unsaturated group-containing compound may be pre-reacted. Pre-reacting can suppress the precipitation of the other unsaturated group-containing compound. The reaction temperature for the pre-reaction is preferably 20 to 200°C, and more preferably 40 to 150°C.

[0065] 〔varnish〕 A varnish according to one embodiment of the present invention comprises the resin composition described above and a solvent.

[0066] Preferably, the solvent is one that can dissolve unsaturated group-containing amino resins or resin compositions. Examples of solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, methyl amyl ketone, isophorone, diisobutyl ketone, diacetone alcohol, and cyclohexanone; N,N-dimethylformamide, N-methyl-2-pyrrolidone; methanol, ethanol, butanol; ethyl acetate, butyl acetate, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate; tetrahydrofuran, toluene, xylene, and anisole. One solvent may be used alone, or two or more may be used in combination. The solvent content is set appropriately depending on the application.

[0067] The solid content concentration of the varnish varies depending on the application, but is preferably 20-80% by mass, and more preferably 50-70% by mass. The solid content concentration of varnish is the ratio of the mass of the varnish excluding the solvent to the total mass of the varnish.

[0068] [Prepreg] A prepreg according to one embodiment of the present invention comprises a fibrous substrate, the aforementioned resin composition, and a curing accelerator. The prepreg may further contain other components.

[0069] The shape of the fibrous base material is not particularly limited and examples include short fibers, yarn, mats, sheets, etc. Examples of fibers constituting the fibrous base material include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, and stainless steel fibers; natural fibers such as cotton, hemp, and paper; and synthetic organic fibers such as polyester resin and polyamide resin. The fibrous base material may be used alone or in combination of two or more types.

[0070] The content of the resin composition is not particularly limited, but is, for example, about 30 to 50% by mass relative to the mass of the fibrous base material.

[0071] Curing accelerators have the effect of promoting the reaction between unsaturated groups. Examples of curing accelerators include imidazole compounds and organic peroxides. Examples of imidazole compounds include 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-vinyl-2-methylimidazole, 1-propyl-2-methylimidazole, 2-isopropylimidazole, 1-cyanomethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl-2-phenylimidazole. Examples of organic peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. In dialkyl peroxides, the alkyl group may be substituted with a phenyl group or the like. An example of such a dialkyl peroxide is dicumyl peroxide. A single curing accelerator may be used alone, or two or more may be used in combination. The curing accelerator content is, for example, about 0.01 to 5.0% by mass relative to the total amount of resin.

[0072] Other components include, for example, curing accelerators, inorganic fillers, solvents, waxes, flame retardants, coupling agents, mold release agents, surface treatment agents, colorants, flexibility enhancers, and epoxy resins. These other components may be used individually or in combination of two or more.

[0073] Prepregs can be manufactured by known methods. For example, a prepreg can be obtained by mixing the aforementioned varnish and a curing accelerator, along with other components as needed, impregnating a fibrous substrate with the resulting mixture, and drying it (removing the solvent).

[0074] [Laminated board] A laminate according to one embodiment of the present invention includes a cured product of the prepreg described above. One embodiment of the laminated board is one comprising a fiber-reinforced resin layer made from the cured prepreg described above. The number of fiber-reinforced resin layers in the laminated board may be one or two or more. The laminate according to this embodiment may further comprise other layers besides the fiber-reinforced resin layer. Examples of other layers include metal foil layers such as copper foil.

[0075] Laminates can be manufactured by known methods. For example, one method involves laminating multiple prepregs as needed, laminating metal foil onto one or both sides of the prepregs or the laminate as needed, and then curing them by heating and pressing. The heating temperature when heating and pressurizing the prepreg is, for example, 60 to 250°C. The pressurizing conditions are, for example, 2 to 20 kN / m. 2 That is the case.

[0076] [Thermosetting molding material] A thermosetting molding material according to one embodiment of the present invention comprises the aforementioned resin composition, a curing accelerator, and an inorganic filler. The thermosetting molding material may further contain other components.

[0077] Examples of hardening accelerators include those mentioned above. The curing accelerator content is, for example, about 0.01 to 5.0% by mass relative to the total amount of resin.

[0078] Examples of inorganic fillers include crystalline silica powder, fused silica powder, quartz glass powder, talc, calcium silicate powder, zirconium silicate powder, alumina powder, and calcium carbonate powder. The inorganic filler content is, for example, about 50 to 90% by mass relative to the total mass of the resin composition.

[0079] Other components include, for example, solvents, curing accelerators, inorganic fillers, solvents, waxes, flame retardants, coupling agents, mold release agents, surface treatment agents, colorants, flexibility enhancers, and epoxy resins. These other components may be used individually or in combination of two or more.

[0080] Thermosetting molding materials can be prepared by mixing a resin composition or varnish with a curing accelerator, an inorganic filler, and other components as needed.

[0081] Thermosetting molding materials can be cured by heating. The heating temperature (curing temperature) for curing thermosetting molding materials is, for example, 60 to 250°C. One example of a curing procedure is to perform pre-curing at the aforementioned preferred temperature for 30 seconds to 1 hour, remove the solvent as necessary, and then perform post-curing at the aforementioned preferred temperature for 1 to 20 hours.

[0082] 〔glue〕 An adhesive according to one embodiment of the present invention comprises the aforementioned resin composition, a curing accelerator, and an inorganic filler. The adhesive may further contain other components.

[0083] Examples of hardening accelerators include those mentioned above. The curing accelerator content is, for example, about 0.01 to 5.0% by mass relative to the total amount of resin.

[0084] Examples of inorganic fillers include those mentioned above. The inorganic filler content is, for example, about 50 to 90% by mass relative to the total mass of the resin composition.

[0085] Other components include, for example, solvents, curing accelerators, inorganic fillers, solvents, waxes, flame retardants, coupling agents, mold release agents, surface treatment agents, colorants, flexibility enhancers, and epoxy resins. These other components may be used individually or in combination of two or more.

[0086] Adhesives, like thermosetting molding materials, can be prepared by mixing a resin composition or varnish, a curing accelerator, an inorganic filler, and other components as needed. Adhesives, like thermosetting molding materials, can be cured by heating. [Examples]

[0087] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. "wt%" means "mass%".

[0088] <Evaluation Method> [Weight average molecular weight (Mw), number average molecular weight (Mn), dispersity (Mw / Mn)] The molecular weight distribution of resins (amino resin, unsaturated group-containing amino resin, and unsaturated group-containing carbonate resin) on a standard polystyrene basis was measured by gel permeation chromatography (GPC), and Mw, Mn, and Mw / Mn were determined. The GPC conditions were as follows: GPC measuring device: Manufactured by Tosoh Corporation, product name "HLC-8120GPC" ("HLC" is a registered trademark of the company). Column: A column formed by linking three columns together (each manufactured by Tosoh Corporation, product names "TSKgel G3000HHR", "TSKgel G2000HHR", and "TSKgel G2000HHR"; "TSKgel" is a registered trademark of the company).

[0089] [Softening point] The softening point of the resin was measured according to the method conforming to JIS K 6910.

[0090] [Glass transition temperature] A molded object was processed to a size of 10.0 mm in width, 5.5 mm in length, and 1.5 mm in thickness, and used as a measurement sample. For this measurement sample, a viscoelasticity measuring device (Hitachi High-Tech Science Co., Ltd., product name "DMA7100") was used to measure tanδ (loss coefficient) in the range of 30°C to 400°C at a frequency of 10 Hz and a heating rate of 2°C / min, and the glass transition temperature Tg was determined from the tanδ. The higher the glass transition temperature, the better the heat resistance.

[0091] [5% thermal decomposition temperature] The molded material was finely ground and used as a sample for measurement. For this sample, a differential thermogravimetric analyzer (Seiko Instruments Inc., product name "TG / DTA6300") was used to measure the thermogravimetric loss in the range of 30 to 800°C at a heating rate of 10°C / min under an atmospheric environment, and the 5% thermal decomposition temperature was determined. The higher the 5% thermal decomposition temperature, the better the heat resistance.

[0092] [Storage modulus] The molded material was processed to a size of 10.0 mm in width, 5.5 mm in length, and 1.0 mm in thickness, and used as a measurement sample. The storage modulus of this measurement sample at 25°C or 250°C at a frequency of 10 Hz was determined using a viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Co., Ltd., product name "DMA7100"). The higher the storage modulus, the better the mechanical strength.

[0093] [Relative permittivity, dielectric loss tangent] A molded object was processed to a size of 3.0 mm in width, 80 mm in length, and 0.8 mm in thickness, and used as a measurement sample. For this measurement sample, the relative permittivity and dielectric loss tangent at a frequency of 10 GHz were determined using the cavity resonance perturbation method with a vector network analyzer (Anritsu Corporation, product name "MS46122B").

[0094] [Measurement of peel strength at 90°C (adhesion test)] From a laminate of molded material and copper foil, excess copper foil was removed so that a 1cm x 10cm area of ​​copper foil remained, and this was used as a measurement sample. The copper foil peel strength of this measurement sample was measured according to the method compliant with JIS C 6481. Specifically, the interface between the copper foil and the molded material was peeled off at a width of 1cm from one end in the longitudinal direction of the copper foil. Using a 90° peeling device (Imada Seisakusho Co., Ltd.: SH-2013 type push-pull stand), the peeled portion of the copper foil was grasped with a gripper and pulled off in a direction perpendicular to the lamination direction, and the strength (copper foil peel strength (unit: N / 10mm)) was measured. The peeling was performed at a tensile speed of 50mm / min and at room temperature (25℃). The higher the copper foil peel strength, the better the adhesion to the copper foil.

[0095] <Synthesis Example 1: Synthesis of Amino Resin 1 using Diphenylamine and Diisopropenylbenzene>

[0096] [ka]

[0097] 132.7 g of diphenylamine was placed in a 500 mL reaction vessel equipped with a thermometer, stirrer, and condenser, and heated to 70°C until dissolved. Then, 5.96 g of p-toluenesulfonic acid monohydrate was placed, the temperature was raised to 165°C, and diisopropenylbenzene was added dropwise over 1 hour. After the dropwise addition was complete, the reaction was allowed to continue at the same temperature for 7 hours, cooled to 100°C, neutralized with sodium hydroxide, and toluene was added to form a varnish. The varnish was repeatedly washed until the pH of the washing solution became neutral to remove ionic impurities. Next, a methanol:water mixture of 9:1 was added to the varnish and stirred, then allowed to stand, and the upper layer was removed. This procedure was repeated four times to purify the varnish until the amount of diphenylamine contained in the varnish was 0.5 area% or less in terms of GPC area%. After that, the solution was concentrated and the solvent was removed by distillation to obtain 97.4 g of amino resin 1. The softening point of the obtained amino resin 1 was 122.0°C. The molecular weight determined by GPC was Mw 3095 and Mn 1578, with an Mw / Mn ratio of 1.96 and a diphenylamine content of 0.2 area%.

[0098] <Synthesis Example 2: Introduction of Styrene Groups into Amino Resin 1>

[0099] [ka]

[0100] In a 500 mL reaction vessel equipped with a thermometer, stirrer, and condenser, 70.0 g of amino resin 1 and 141.4 g of N-methyl-2-pyrrolidone were charged and heated to 60°C to dissolve. Next, 6.29 g of potassium hydroxide was charged and the temperature was raised to 95°C, after which 15.6 g of chloromethylstyrene was added dropwise over 1 hour. After the dropwise addition was complete, the reaction was carried out at the same temperature for 12 hours, and then cooled to 30°C. 1.28 g of oxalic acid dihydrate was added to this reaction solution to neutralize it, and 140 g of methyl isobutyl ketone was added. The mixture was washed with water until the pH of the washing solution became neutral, yielding 141.7 g of varnish containing unsaturated group-containing amino resin 1 (non-volatile content: 64.5 g). The obtained unsaturated group-containing amino resin 1 had a molecular weight of Mw 3334 and Mn 1837, with an Mw / Mn ratio of 1.82 and a styrene modification rate of 20%. The theoretical unsaturated group equivalent calculated from the styrene modification rate was 1557 g / eq.

[0101] <Synthesis Example 3: Synthesis of Amino Resin 2 using Diphenylamine and Cyclohexane Carboxaldehyde>

[0102] [ka]

[0103] 188.6 g of diphenylamine and 500.0 g of toluene were charged into a 1000 mL reaction vessel equipped with a thermometer, stirrer, and condenser, and dissolved. Next, 8.48 g of p-toluenesulfonic acid monohydrate was charged, and 100.0 g of cyclohexanecarboxyaldehyde was added. The temperature was raised to 85°C and the reaction was carried out at the same temperature for 8 hours. The reaction solution was cooled to 40°C, and NaOH was added for neutralization. Washing was repeated until the pH of the washing solution became neutral. Next, 1731.6 g of methanol was charged into a 3 L flask equipped with a thermometer, stirrer, and condenser, and the washed reaction solution was added dropwise to reprecipitate the resin. The precipitate was collected by filtration, washed again with methanol, and then 300.0 g of anisole was added to varnish it. After that, the solution was concentrated and the solvent was removed by distillation to obtain 125.1 g of amino resin 2. The softening point of the obtained amino resin 2 was 183.1°C. The molecular weight determined by GPC was Mw 4702 and Mn 1982, with a Mw / Mn ratio of 2.37.

[0104] <Synthesis Example 4: Introduction of Vinylbenzyl Groups into Amino Resin 2>

[0105] [ka]

[0106] In a 500 mL reaction vessel equipped with a thermometer, stirrer, and condenser, 110.0 g of amino resin 2 and 378.1 g of N-methyl-2-pyrrolidone were charged and heated to 60°C to dissolve. Next, 7.74 g of potassium hydroxide was charged and the temperature was raised to 95°C, after which 18.1 g of vinyl benzyl chloride was added dropwise over 1 hour. After the addition was complete, the reaction was carried out at the same temperature for 12 hours, and then cooled to 30°C. 2.48 g of oxalic acid dihydrate was added to this reaction solution to neutralize it, and 180 g of methyl isobutyl ketone was added. The mixture was washed with water until the pH of the washing solution became neutral. Next, 1000.0 g of methanol was charged into a 3 L flask equipped with a thermometer, stirrer, and condenser, and the washed reaction solution was added dropwise to reprecipitate the resin. The precipitate was collected by filtration, washed again with methanol, and then dried under reduced pressure to obtain 111.2 g of unsaturated group-containing amino resin 2. The molecular weight of the obtained unsaturated group-containing amino resin 2 was Mw 5811, Mn 2291, Mw / Mn 2.54, and the vinylbenzyl modification rate was 18%. The theoretical unsaturated group equivalent calculated from the vinylbenzyl modification rate was 1552 g / eq.

[0107] <Synthesis Example 5: Synthesis of unsaturated group-containing carbonate resin using diphenyl carbonate, tricyclodecanedimethanol, and 2-allylphenol> 1000.0 g of diphenyl carbonate and 687.2 g of tricyclodecanedimethanol were charged into a 3 L reaction vessel equipped with a thermometer, stirrer, and condenser, and melted and mixed at 100°C. Then, 0.6 g of 48% KOH was added, and the system was slowly reduced to 10 mmHg while reacting at 200°C for 4 hours. Next, after cooling to 150°C, 375.8 g of 2-allylphenol was added, and the system was again slowly reduced to 10 mmHg while reacting at 200°C for 2 hours. Then, 1500 g of methyl isobutyl ketone was added, neutralized with 35% hydrochloric acid, washed with water, and the remaining phenol and 2-allylphenol were concentrated to obtain unsaturated group-containing carbonate resin 1 with an alicyclic skeleton. The softening point of the obtained resin was 65.8°C. The molecular weight determined by GPC was Mw 1970, Mn 948, and Mw / Mn was 2.08. The unsaturated group equivalent of the obtained resin was set to 474 g / eq, which is half the amount of Mn. The tricyclodecanedimethanol content determined by GPC was 0.35 area%.

[0108] <Example 1> [Preparation of resin varnish] 62.4 g of unsaturated group-containing amino resin 1 (unsaturated group equivalent: 1557 g / eq) obtained in Synthesis Example 2 and 45.0 g of bisphenol A diphenyl ether bismaleimide (manufactured by Yamato Chemical Industries, Ltd.: BMI-4000, unsaturated group equivalent: 285 g / eq) were dissolved in toluene to obtain a resin varnish with a solid content of 50 wt%.

[0109] [Manufacturing of molded products] The prepared resin varnish was heated to 135°C while removing toluene under reduced pressure at 40 mmHg. Dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd.: Permil D) was added as a catalyst at a concentration of 1.0 wt% relative to the total resin amount, and the entire amount of toluene was removed by distillation to obtain a curable composition. The obtained curable composition was poured into a mold with a thickness of 1 mm and a size of 10 cm x 10 cm, pressed at 200°C, and then after-baked at 230°C for 5 hours to obtain a molded product. The total resin amount refers to the sum of the unsaturated group-containing amino resin and other unsaturated group-containing compounds.

[0110] [Fabrication of laminates] The curable composition obtained in the same manner as described in [Preparation of Molded Product] above was poured into a mold measuring 1 mm thick and 10 cm x 10 cm. A 12 cm x 10 cm piece of copper foil (manufactured by JX Metals Corporation: JTC-1 / 20z) was placed on top of the mold so that its shiny surface was in contact with the curable composition. After press molding at 200°C, an after-bake was performed at 230°C for 5 hours to obtain a laminate of the molded product and the copper foil.

[0111] <Example 2> A resin varnish was prepared in the same manner as in Example 1, except that 83.2 g of unsaturated group-containing amino resin 2 (unsaturated group equivalent: 1552 g / eq) obtained in Synthesis Example 4 was used instead of 62.4 g of unsaturated group-containing amino resin 1 (unsaturated group equivalent: 1557 g / eq), and 45.0 g of bisphenol A diphenyl ether bismaleimide (manufactured by Yamato Chemical Industries, Ltd.: BMI-4000, unsaturated group equivalent: 285 g / eq) was replaced with 60.0 g. Molded articles and laminates were then produced.

[0112] <Example 3> 56.26 g of unsaturated group-containing amino resin 1 (unsaturated group equivalent: 1557 g / eq) obtained in Synthesis Example 2 was dissolved in toluene to a solid content of 50 wt% to obtain a resin varnish. Molded articles and laminates were prepared in the same manner as in Example 1, except that this resin varnish was used.

[0113] <Example 4> A resin varnish was prepared in the same manner as in Example 3, except that 64.79 g of the unsaturated group-containing amino resin (unsaturated group equivalent: 1552 g / eq) obtained in Synthesis Example 4 was used instead of 56.26 g of the unsaturated group-containing amino resin 1 (unsaturated group equivalent: 1557 g / eq). Molded articles and laminates were then produced.

[0114] <Comparative Example 1> Resin varnish was prepared in the same manner as in Example 1, except that 162.34 g of unsaturated group-containing carbonate resin (unsaturated group equivalent: 474 g / eq) obtained in Synthesis Example 5 was used instead of 56.26 g of unsaturated group-containing amino resin 1 (unsaturated group equivalent: 1557 g / eq), and 43.74 g of bisphenol A diphenyl ether bismaleimide (manufactured by Yamato Chemical Industries, Ltd.: BMI-4000, unsaturated group equivalent: 285 g / eq) was changed to 37.57 g. Molded articles and laminates were then produced.

[0115] <Comparative Example 2> A resin varnish was prepared in the same manner as in Example 1, except that 82.7 g of OPE-2St (polyphenylene ether modified with styroyl groups at both ends, equivalent to 590 g / eq) manufactured by Mitsubishi Gas Chemical Company, Inc. was used instead of 56.26 g of unsaturated group-containing amino resin 1 (equivalent to 1557 g / eq of unsaturated groups), and 43.74 g of bisphenol A diphenyl ether bismaleimide (manufactured by Yamato Chemical Industries, Ltd.: BMI-4000, equivalent to 285 g / eq of unsaturated groups) was changed to 40.0 g. Molded articles and laminates were then produced.

[0116] For each example of molded material, the glass transition temperature, 5% weight loss temperature, storage modulus, dielectric constant, and dielectric loss tangent were measured, and the copper foil peel strength was measured for each example of laminate. The results are shown in Table 1. In Table 1, "E+n" in the value of the storage modulus is "×10 n This means "3.9E+09" is equivalent to "3.9 × 10 9 "

[0117] [Table 1]

[0118] The molded (cured) products obtained in Examples 1-3 had low dielectric loss tangents. They also exhibited sufficiently low dielectric constants, good heat resistance, mechanical strength, and good adhesion to copper foil. In particular, Examples 1-2, which combined an unsaturated group-containing amino resin with other unsaturated group-containing compounds, showed excellent dielectric properties and adhesion to copper foil. On the other hand, Comparative Example 1, which used unsaturated group-containing carbonate resin 1 instead of unsaturated group-containing amino resin, had good adhesion to the copper foil because it contained the polar group carbonate group, but its dielectric loss tangent was higher than that of Examples 1 to 3. Comparative Example 2, which used OPE-2St instead of the unsaturated group-containing amino resin, showed inferiority to Examples 1-3 in both dielectric loss tangent and adhesion to copper foil.< / n>

Claims

1. The following formula (1): 【Chemistry 1】 (In equation (1), n ​​is an integer greater than or equal to 1, and R １ The following equation (2): 【Chemistry 2】 [In formula (2), R ３ This is an organic group having at least one unsaturated group selected from the group consisting of vinylbenzyl group, alkenyl group having 2 to 20 carbon atoms, acryloyl group and methacryloyl group, or a hydrogen atom, Ar １ is a phenylene group or a naphthylene group, Ar ２ is a phenylene group, a naphthylene group, or the following formula (3): 【Transformation 3】 [In formula (3), R ４ is an organic group having the unsaturated group or a hydrogen atom, and Ar ３ and Ar ４ These are, independently, either a phenylene group or a naphthylene group. This is the base represented by [this symbol]. is a group represented by, and R ２ is a crosslinking group. When n is 2 or more, the n R １ may be the same or different, and the n R ２ may be the same or different. ) Includes a structure represented by, R in the structure represented by formula (1) ３ and R ４ An unsaturated group-containing amino resin, wherein at least a portion of it is an organic group having the unsaturated group.

2. In equation (1) above, n is an integer greater than or equal to 2, R in the structure represented by formula (1) ３ and R ４ The unsaturated group-containing amino resin according to claim 1, wherein a portion of the group is a hydrogen atom.

3. R in formula (1) ２ The following equation (5): 【Chemistry 4】 (In formula (5), R ５ and R ６ Each of these is independently a hydrogen atom, a cycloalkyl group having 3 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an aryl group having 6 to 16 carbon atoms, or a heterocyclic group having 3 to 16 carbon atoms, or R ５ and R ６ It forms a ring together with the carbon atom to which it is bonded. The cycloalkyl group, the aryl group, and the heterocyclic group may have at least one substituent selected from the group consisting of a halogen atom, a nitro group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, a carboxyl group, and a hydroxyl group. A base represented by the following formula (6): 【Transformation 5】 (In formula (6), R ７ , R ８ , R ９ and R １０ (Each of these is independently either a hydrogen atom or a methyl group.) The unsaturated group-containing amino resin according to claim 1, wherein the group is represented by the group.

4. R in formula (1) ２ This is represented by formula (5) above, and R in formula (5) above ５ is a hydrogen atom, R ６ The unsaturated group-containing amino resin according to claim 3, wherein is a cycloalkyl group, an alkyl group, or an aryl group, or a group represented by formula (6).

5. Ar in formula (2) １ and Ar ２ The unsaturated group-containing amino resin according to claim 1, wherein each of the groups is a phenylene group.

6. A resin composition comprising an unsaturated group-containing amino resin according to any one of claims 1 to 5, and an unsaturated group-containing compound other than the unsaturated group-containing amino resin.

7. The resin composition according to claim 6, wherein the unsaturated group-containing compound is at least one selected from the group consisting of maleimide group-containing compounds and butadiene-styrene oligomers.

8. A varnish comprising the resin composition according to claim 6 and a solvent.

9. A prepreg comprising a fibrous substrate, the resin composition according to claim 6, and a curing accelerator.

10. A laminate containing a cured prepreg according to claim 9.

11. A thermosetting molding material comprising the resin composition according to claim 6, a curing accelerator, and an inorganic filler.

12. An adhesive comprising the resin composition according to claim 6, a curing accelerator, and an inorganic filler.

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